Polymers of 1-butene-2,3,4-tricarboxylic acid

ABSTRACT

A water soluble salt of an aliphatic polycarboxylic acid useful as a detergent builder, and having the formula:

United States Patent [191 Chakrabarti et a].

[54] POLYMERS OF l-BUTENE-2,3,4-

TRICARBOXYLIC ACID [75] Inventors: Paritosh M. Chakrabarti, Highstown;Hugo Stange; Gert Paul Volpp, both of Princeton, all of NJ.

[73] Assignee: FMC Corporation, New York, N.Y.

[22] Filed: Aug. 11, 1970 [21] Appl. No.: 63,023

[52] [1.8. CI. ..260/78.5 R, 252/89, 252/121, 252/132, 252/135, 252/138,260/784 R,

[5 1] Int. Cl. ..C08f 15/36 [58] Field of Search ..260/78.4 R, 78.4 E,78.5 R, 260/785 B, 78.5 E, 537 R, 485 R [56] References Cited UNITEDSTATES PATENTS 2,782,227 2/1957 Dazzi ..260/485 3,463,734 8/1969 Carteret al. ..252/99 FOREIGN PATENTS OR APPLICATIONS 1,539,973 9/1968 France..260/78.5

[ 51 Feb. 20, 1973 Primary Examiner-James A. Seidleck AssistantExaminerJohn Kight, Ill

AttorneyRobert D. Jackson, Eugene G. Seems and Pauline Newman [57]ABSTRACT A water soluble salt of an aliphatic polycarboxylic acid usefulas a detergent builder, and having the formula:

wherein each of m and n can be zero or a positive number, it beingprovided that the sum of m and n is always less than one; p is aninteger the upper limit of I which is determined by the solubility ofthe salts in an 6 Claims, No Drawings POLYMERS OF 1BUTENE-2,3,4-TRICARBOXYLIC ACID BACKGROUND OF THE INVENTION A. Field ofthe Invention This invention relates to cleansing and launderingcompositions. It is particularly concerned with such compositionscontaining a polyelectrolyte builder material which enhances thecleansing action of detergents.

B. Description of the Prior Art In the cleansing art, it is known thatthe detergency level of soaps and synthetic surfactants can be increasedby the use of certain materials commonly referred to as builders. Suchcleansing fortifiers make possible the attainment of superior cleaningperformance and at lower cost than can be realized with the so-callednon-built detergent compositions.

The mechanism by 'which builders enhance the cleansing action ofdetergents is not fully understood, although, several explanations havebeen advanced. However, none of the theories thus far advocated enableone to predict accurately which class of compounds possesses usablebuilder properties and which compounds do not. In short, the builtdetergent art is still in the empirical stage.

The lack of any satisfactory theory concerning builder behavior may beexplained, at least in part, by the complex nature of detergency and thecountless factors which contribute to overall performance. It isgenerally agreed that builder compounds exhibit at least some effect insuch areas as stabilization of solid soil suspension, emulsification ofsoil particles, the surface activity of aqueous detergent solutions,solubilization of water-insoluble materials, foaming or sudsproducingcharacteristics of the washing solution, peptization of soilagglomerates, neutralization of acid soil, and the inactivation ofmineral constituents present in the washing solution. Thus, anytheoretical discussion of the boosting capacity of a builder compoundshould give due consideration to all the significant individual actionsinvolved in the detergent process and must apply equally to all theusual conditions of soiling and washing.

Builder materials should exhibit certain ancillary properties in orderto be acceptable in current washing processes and consumer marketingtechniques. Thus, a builder should preferably be white, inexpensive,nontoxic, stable to oxidizers in the dry state, non-corrosive,non-hygroscopic, stable to hot alkaline detergent solutions and stableduring spray drying operations.

Examples of known inorganic builder materials are the water-soluble,inorganic alkaline builder salts which can be used alone or incombination, including alkali metal carbonates, borates, phosphates,polyphosphates, bicarbonates and silicates.

Examples of known organic builder materials are alkali metal, ammoniumor substituted ammonium aminopolycarboxylates, e.g., sodium andpotassium ethylenediaminetetraacetate, sodium and potassiumN(2-hydroxyethyl)-ethylenediaminetriacetate, sodium and potassium andtriethanolammonium N (2- hydroxyethyl) nitrilodiacetate. Alkali metalsalts of phytic acid, e.g., sodium phytate, are also suitable as organicbuilders.

Although the condensed inorganic polyphosphates find the widestcommercial acceptance, these exhibit the undesirable property ofhydrolyzing into less condensed phosphorus compounds which areessentially devoid of builder properties. Moreover, these hydrolyticderivatives often form undesirable precipitates in aqueous washingsolutions. Such lower forms include orthophosphate.

Recently, a great deal of interest has focused on the polyelectrolytebuilder materials which are highly polar polymers such as thewater-soluble salts of aliphatic polycarboxylic acids. Examples of theseclasses of builders are disclosed in U.S. Pat. No. 3,308,067 to Diehland U.S. Pat. No. 3,463,734 to Carter Jr. et al. These new types ofbuilders do not hydrolyze into undesirable by-products.

Manifestly, the detergent and cleansing industry is still activelysearching for more effective builder materials and accordingly work isproceeding apace toward uncovering new and more effective classes ofthese valuable entities.

SUMMARY OF THE INVENTION It has now been discovered that excellentbuilder properties are exhibited by a novel class of aliphaticpolycarboxylic acids of the formula wherein each of m and n can be zeroor a positive number, it being provided that the sum of m and n isalways less than one; p is an integer the upper limit of which isdetermined by the solubility of the salts in an aqueous system; X isderived from the monomer l-butene-2,3,4-tricarboxylic acid and Y and Zare each derived from a monoethylenically unsaturated monomer containing1 to 3 substituents selected from the class consisting of carboxy, lowercarboxyalkyl, lower alkyl, lower chloroalkyl, 'hydroxy, non-gem.dihydroxy, lower acyloxy, chloro, and lower alkoxy, it being providedthat any one of the carboxy groups can be esterified with a loweraliphatic radical. The provision of the novel builders, aforesaidincluding the preparation and their use in cleansing compositions,constitutes the principal objects and purpose of the invention. Otherobjects and purposes will become apparent.

DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS As can be seenfrom an inspection of the formula aforesaid, the polymeric buildercompounds of the invention are polymers of l-butene-2,3,4-tricarboxylicacid or copolymers thereof with l or 2 monoethylenically unsaturatedmonomers. The polymerization is carried out in the manner of preformingethylenic polymerizations, details of which are given below. Generallyspeaking, such polymerization is effected under free radical producingconditions, commonly provided by the use of peroxides such as alkalimetal persulfates or an organic peroxide such as benzoyl peroxide. Thepolymerization may be solution polymerization or emulsion polymerizationdepending on the solubility of the monomer starting materials. In someinstances bulk polymerization is preferred.

In the case of copolymers, the ratio of l-butene- 2,3 ,4-tricarboxylicacid with other ethylenic monomers is governed by the requirement thatthe copolymer must form water soluble salts or at least be soluble inthe cleansing composition. Accordingly, the copolymer must containsolubilizing groups. These are preferably carboxy groups which can comesolely from the l-butene-2,3,4-tricarboxylic acid or from a combinationof the latter with at least one of the ethylenic units. There is atendency toward insolubility when the number of non-carboxy containingunits greatly exceeds the carboxy containing units. The minimal percentof carboxy carrying groups needed for water solubility will vary to someextent depending upon the polar character of the substituents attachedto the ethylenic units. Thus, where the latter contain other hydrophilicgroups, the desired water solubility can be realized with a relativelysmall percentage of carboxy groups in the copolymer whereas more carboxygroups will be needed if the associated ethylenic groups carry non-polarsubstituents such as alkyl radicals. Those skilled in the art willgenerally be able to adjust the ratio of monomer units to achieve thedesired solubility.

Typical of the polymeric compounds described herein are the following:homopolymer of l-butene- 2,3,4-tricarboxylic acid; 1:1, 1:2, and 2:1copolymers of l-butene-2,3,4-tricarboxylic acid and itaconic acid; 1:1,1:2, and 2:1 copolymers of l-butene-2,3,4-tricarboxylic and methacrylicacid; 1:1, 1:2, and 2:1, copolymers of l-butene-2,3,4-tricarboxylic acidand acrylic acid; 1:1 copolymer of l-butene-2,3,4-tricarboxylic acid andmaleic acid; 1:1 copolymer of l-butene-2,3,4-tricarboxylic acid andvinyl acetate, 1:1 copolymer of l-butene-2,3,4-tricarboxylic acid andvinyl alcohol; 5:2 copolymer of l-butene-2,3,4-'tricarboxylic acid andmethyl vinyl ether; 1:1 copolymer of 1-butene-2,3,4-tricarboxylic acidand vinyl chloride; 1:1:1 copolymer of l-butene-2,3,4-tricarboxylicacid, itaconic acid and acrylic acid; 1:1:1 copolymer ofl-butene-2,3,4-tricarboxylic acid, maleic acid and acrylic acid; and1:1:l copolymer of l-butene- 2,3,4-tricarboxylic acid, itaconic acid andmaleic acid; wherein the ratios mentioned are molar ratios.

Preferred compounds are l:l:l copolymer of l-butene-2,3,4-tricarboxylicacid, itaconic acid, and acrylic acid; 1:], 1:2, and 2:1 copolymers ofl-butene-2,3,4- tricarboxylic acid and itaconic acid; 1:1, 1:2, and 2:1copolymers of 1-butene-2,3,4-tricarboxylic acid and acrylic acid.

The structural features of the operable and preferred polymers andcopolymers have, as a matter of convenience, been defined herein interms of the carboxylic-acid containing monomers from which suchpolymers and copolymers theoretically can be derived. It is recognized,however, that in many cases it is desirable or even preferable to formsuch polymers and copolymers in practice by employing derivatives orprecursors of such carboxylic-acid-containing monomers in thepolymerizations leading to the desired polymers and copolymers. Thus,the monomeric species employed, can in many cases, be such derivativesor precursors of the designated acids as the anhydrides, the full orpartial esters of such acids, amides, nitriles, etc., or mixtures ofsame, which after polymerization can be converted to the carboxylatesalts by appropriate chemical reactions.

The degree of polymerization, p, of the novel polyelectrolyte buildercompounds of this invention has a significant and practical bearing onthe builder effectiveness of these compounds. The lower limit for p hasbeen established as three resulting in compounds having a molecularweight on the order of not less than about 350. Builder properties ofthe compounds of this invention drop off substantially as the molecularweight goes below 350.

It is somewhat more difficult to establish an absolute value for anupper limit of the degree of polymerization above which thepolyelectrolyte builder compounds no longer function as efficientbuilders. The fact is that practical considerations appear to be theprimary determining factor as the degree of polymerization increases.For instance, as the molecular weight of a polymeric material increases,it is generally acknowledged that the water solubility thereofdecreases. In general, the present invention that the polyelectrolytebuilder compounds must be adequately soluble in the washing solutionunder regular usage conditions.

Recommended builder concentrations generally range from about 0.01percent to about 0.50 percent by weight of the washing solution. Theupper operable limit, therefore, so far as the scope of this inventionis concerned, is reached when it is no longer possible to get enough ofthe builder compound into solution to act as a builder.

The higher builder concentrations on the order of 0.50 percent by weightmay be found necessary under certain washing conditions such as a waterhardness of 21 grains equivalent CaCO per gallon or higher. In suchsituations, any of the polyelectrolyte builder compounds of thisinvention could be selected whose solubility characteristics would allowa builder concentration in an aqueous solution to the necessary amount.in more general household situations, builder concentrations of 0.03percent to about 0.06 percent are found to be adequate.

It can be appreciated, according to the preceding discussion, that thedegree of polymerization of these compounds can very within a very widerange. Generally, however, the degree of polymerization, p, can bewithin the ranges of 3 to about 5,000. This corresponds to a molecularweight range for the compounds of this invention from 350 to about1,500,000. A preferred range for the degree of polymerization, p, isfrom about 4 to about 500. This represents a preferred molecular weightrange for the polyelectrolyte builder compounds of this invention ofabout 500 to about 175,000.

It is difficult to accurately determine molecular weights of polymericcompounds. Such figures will generally very depending upon the methodused to determine them. It is widely recognized, for instance, that anymolecular weights of polymeric materials which are given by manufacturesconstitute an average of the molecular weights of the molecules present.Moreover, molecular weight ranges are usually given which vary widelydepending again upon the method used to measure the molecular weights.Among the several methods frequently used to measure molecular weightsof polymeric compounds are osmometry, molecular weight determination byend-group analysis, cryoscopy, ebullioscopy, light-scattering, gelpermeation chromatography, and ultracentrifuge. Each of these methodsare presently in varying degrees of development and each one has specialtypes of polymeric compounds to which it is best adapted.

The minimum molecular weight of 350 mentioned above was arrived atempirically and, to a great extent, is based on the knowledge andexperience acquired from working with these polyelectrolyticpolycarboxylic polymers.

Viscosity is a property more frequently used by polymer chemists thanmolecular weights in characterizing polymeric compounds. This is nodoubt due to the comparatively easier and less complicated methodsavailable for obtaining viscosity data. To make such data meaningful, itis necessary to also give the test conditions under which themeasurements were run. Since there is a recognized correlation betweenthe viscosity of polymeric compounds and their molecular weights andsince such figures can be more meaningful and can frequently be moreavailable than molecular weights, the polymeric builder compounds usedin the examples of this invention are characterized in terms of specificviscosity. In all cases the viscosity characterization corresponds to amolecular weight substantially above 350.

According to this invention extraordinary cleaning results can beobtained by using the above polyelectrolyte builder compounds with awide range of surface active materials and mixtures thereof. The buildercompounds are effective when used alone or in coadmixture with otherknown builders.

In general, the detergent compositions of this invention, the essentialingredients are (a) an organic water soluble detergent surface activematerial as defined and illustrated below and (b) a novelpolyelectrolyte builder compound meeting the structural requirementsspecified and exemplified above. The detergent compositions of thisinvention, therefore, contain the essential ingredients in a ratio ofpolyelectrolyte builder to detergent surfactant in the range of about1:3 to about :1 by weight, with such compositions providing in aqueoussolution a pH of about 8 to about 12. The preferred ratio ofpolyelectrolyte builder to detergent surfactant is about 1:2 to about5:1 and the optimum pH range is 9.5 to about 11.5.

The organic detergent compounds, i.e. surface active agents, which canbe utilized in the compositions of this invention are anionic, nonionic,ampholytic and'zwitterionic synthetic detergents and mixtures thereofand are exemplified as follows:

A. Anionic synthetic non-soap detergents can be broadly described as thewater-soluble salts, particularly the alkali metal salts, of organicsulfuric reaction products having in their molecular structure an alkylradical containing from about eight to about 22 carbon atoms and aradical selected from the group consisting of sulfonic acid and sulfuricacid ester radicals. Important examples of the synthetic detergents arethe sodium or potassium alkyl sulfates, sodium or potassiumalkylbenzenesulfonates, in which the alkyl group contains from aboutnine to about carbon atoms (the alkyl radical can be a straight orbranched aliphatic chain); alkyl (glycerylsulfate) ether; sodium coconutoil fatty acid monoglyceride sulfates and sulfonates; sodium orpotassium salts or sulfuric acid esters of the reaction product of onemole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols)and about 1 to 6 moles of ethylene oxide, sodium or potassium salts ofalkyl phenol ethylene oxide ether sulfate with about 1 to about 10 unitsof ethylene oxide per molecule and in which the alkyl radicals containfrom eight to about 12 carbon atoms: the reaction product of fatty acidsesterified with isothionic acid and neutralized with sodium hydroxide,sodium or potassium salts of fatty acid amide of a methyl tauride, andsulfonated olefins.

b. Nonionic synthetic detergents: One class can be broadly defined ascompounds produced by the condensation of alkylene oxide groups(hydrophilic in nature) with an organic hydrophobic compound, which maybe aliphatic or alkyl aromatic in nature. The length of the hydrophilicor polyoxyalkylene radical which is condensed with any particularhydrophobic group can be readily adjusted to yield a water-solublecompound having the desired degree of balance between hydrophilic andhydrophobic elements. Another class has semi-polar characteristics.Preferred classes of nonionic synthetic detergents are as follows:

1. A class of nonionic synthetic detergents under the trade name ofPluronic. These compounds are formed by condensing ethylene oxide with ahydrophobic base formed by the condensation of propylene oxide withpropylene glycol;

2. The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about six to 12 carbon atoms in either a straight chain or branchedchain configuration with ethylene oxide;

3. Those nonionic synthetic detergents derived from the condensation ofethylene oxide with the product resulting from the reaction of propyleneoxide and ethylene diamine;

4. The condensation product of aliphatic alcohols having from eight to22 carbon atoms, in either straight chain or branched chainconfiguration, with ethylene oxide;

5. The ammonia, monoethanol and diethanol amides of fatty acids havingan acyl moiety of from about eight to about 18 carbon atoms;

6. Long chain tertiary amine oxides such as dimethyldodecylamine oxide;cetyldimethylamine oxide; bis-(2-hydroxyethyl)-dodecylamine oxide;bis-(2- hydroxyethyl)-3 -dodecoxyl -hydroxypropylamine oxide;

7. Long chain tertiary phosphine oxides such as dimethyldodecylphosphineoxide; diethyldodecylphosphine oxide; dimethyl-, (2-hydroxydodecyl)phosphine oxide; I

8. Long chain sulfoxides such as dodecyl methyl sulfoxide;3-hydroxytridecyl methyl sulfoxide; 3- methoxytridecyl methyl sulfoxide;3-hydroxy-4- dodecoxybutyl methyl sulfoxide.

c. Ampholytic synthetic detergents can be broadly described asderivatives of aliphatic secondary and tertiary amines, in which thealiphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents contains from about eight to 18 carbon atomsand one contains an anionic water solubilizing group, e.g., carboxy,sulfo, sulfato, phosphate, or phosphono. Examples of compounds fallingwithin this definition are sodium-3-dodecylaminoproprionate andsodiumi3-dodecylaminopropanesulfonate.

d. Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniumcompounds, in which the aliphatic radical may be straight chain orbranched, and wherein one of the aliphatic substituerrts contains fromabout eight to 18 carbon atoms and one contains an anionic watersolubilizing group; e.g., carboxy, sulfo, sulfato, phosphato, orphosphono. Examples of compounds falling within this definition are 3-(N ,N -dimethyl-N-hexadecylammonio)propane-1 -sulfonate and3-(N,N-dimethyl-N-hexadecylammonio)-lhydroxy propanel -sulfonate.

In the novel detergent formulations of this invention, the weight ratioof surface active agent to builder ranges from about 3:1 to 1:10. Thesetwo ingredients generally represent at least about 45 percent of thetotal detergent formulation.

It should be noted that the novel builders herein are used either in theform of their alkali metal salts or in acid-form together with asufficient quantity of an alkali metal base, such as the carbonate orhydroxide, in order to neutralize the carboxyl group and adjust the pHlevel of the final detergent solution to within the desired 9.5-1 1.5range.

The formulations may also contain minor amounts of optional additives inorder to modify certain properties thereof. Among such optionaladditives are included: foam builders and stabilizers, antiredepositionagents such as sodium carboxymethylcellulose, corrosion in hibitors suchas benzotriazole, optical brighteners, bactericides, perfumes, bleaches,enzymes, dyes, blueing agents, inorganic salts, solvents and the line,These total optional ingredients commonly range from about 30 percent toabout 55 percent, by weight of the formulation.

Methods for preparing detergent formulations are well known to thoseskilled in the art, a typical method involving drying the ingredients,forming them into an aqueous slurry and then spray drying. The finaldetergent formulations may be a mixture of dry ingredients, aconcentrated aqueous solution or a solid mix resulting from the dryingthereof, or a combination of dry solids and dry ingredients as is commonin the art.

The following examples will further illustrate the embodiment of thisinvention. In these examples, all parts given are by weight unlessotherwise noted.

EXAMPLE 1 l-Butene-2,3,4-tricarboxylic Acid-ltaconic Acrylic Acid(1:1:1) Copolymer A solution of l-butene-2,3,4-tricarboxylic acid (4.7g), itaconic acid (3.25 g), and acrylic acid (1.8 g) in freshlydistilled water (20 ml) was placed in 50 ml polymerization bottle fittedwith a rubber septum. A solution of potassium persulfate (0.08 g) inwater (4 ml) was injected through the rubber septum, and the aqueousmixture degassed by repeated freezing and evacuation. Then a solution ofsodium metabisulfite (0.04 g) in water (4 ml) was injected. The bottlewas warmed to room temperature, filled with nitrogen and the contentsstirred until a clear solution resulted (5 days). The solution wasconcentrated to half its original volume in vacuo and the polymerprecipitated by pour- Aciding the concentrated solutions into acetone (1liter). The white precipitate was filtered and washed five times with 20ml portions of warm acetone and then dried at 65/.l mm for 2 hr. Yield:6 g.

EMULSION POLYMERIZATION This procedure was used for homeandcopolymerizing water insoluble oils, i.e., esters ofalkenepolycarboxylic acids. An emulsifier solution was first prepared bymixing the following:

Santomerse-3 (65% active, Monsanto) 20 g Brij-35 active, Atlas Chemicals15 g Dupanol ME (100 active, duPont) 25 g Cellosize WP-4400 (UnionCarbide) 2.4 g Distilled Water 500 ml The ester of the unsaturatedalkenepolycarboxylic acid or a mixture of it with other oily waterinsoluble vinylic monomer was emulsified in about the same volume of theemulsifier solution. Then about 0.15 times the total volume of emulsionof 2.8 percent aqueous potassium persulfate was added as an initiatoralong with, if desired, an equal volume of 2.8 percent sodiummetabisulfite solution. The pH of the solution was then adjusted to 3-5by adding 5 percent sodium bicarbonate solution. The mixture was chargedinto a polymerization bottle fitted with a rubber septum, degassed asdescribed under Example 1 and shaken for 24-150 hr., when a waxy lump ofsolid had formed. The solid lump was removed, washed successively withwater and then dried at 65/0.1 mm..

The following example is illustrative.

EXAMPLE 2 l-lomopoly(Trimethyl l-Butene-2,3 ,4-tricarboxylate) Trimethyll-butene-2,3 ,4-tricarboxylate (7.7 g),

emulsifier solution (6.5 ml), 2.8 percent potassium persulfate solution(1.9 ml), 2.8 percent sodium metabisulfite solution (1.9 ml), and 5percent sodium bicarbonate solution (0.4 ml) were charged, in the aboveorder, into a polymerization bottle. The bottle was closed with a rubberseptum and the contents degassed by repeating freezing and evacuation asdescribed before. The bottle was mechanically shaken for six days andthe white waxy solid that had separated was washed repeatedly with waterand dried at 65/0.1 mm; yield, 6 g.

Solution Polymerization in Organic Solvents The material or materials tobe polymerized along with a chain transfer agent such as laurylmercaptan, if required, was dissolved in 2-4 times the volume ofbenzene, toluene, xylene, or dioxan, and heated to reflux in anatmosphere of nitrogen. A solution of the catalyst (usually benzoylperoxide) in the same solvent was then added dropwise to the reactionmedium. The boiling was continued until the polymer separated as aninsoluble material (1-5 hr.). It was washed repeatedly with the samesolvent and dried at 65I0.1 mm. The following preparation will serve asan example.

EXAMPLE 3 Copoly(Trimethyl (Trimethyl1-Butene-2,3,4-tricarboxylate-ltaconic Anhydride) 1:1

A solution of trimethyl l-butene-2,3,4-tricarboxylate (11.5 g) anditaconic anhydride (5.6 g) in dry benzene (60 ml) was heated to boilingunder reflux in an atmosphere of nitrogen. A solution of benzoylperoxide (0.8 g) in benzene (30 ml) was added in three equalinstallments at 1 hr. intervals. After a total of 4 hr. boiling, thepolymer that had separated was removed from the solution, washed fivetimes with warm benzene and dried at 65/0.l mm; yield, 8 g.

Bulk Polymerization This procedure was applicable to the esters oranhydrides of the monomeric acids. The material or mixture of materialsto be polymerized was intimately mixed with the initiating catalyst andtaken in a thick round bottomed flask containing a stirring magnet. Theflask was closed with a rubber septum and its charge degassed usingsimilar procedure as described under Example 1. The flask was thenheated at the desired temperature with magnetic stirring until aconsiderable rise in viscosity occurred and the stirrer stopped. Theunreacted monomers were then removed under a pressure of 0.1 mm up to atemperature of 180. In an alternative procedure, used when one of themonomers was highly volatile, instead of a round bottomed flask closedwith a rubber septum, a thick walled sealed tube protected with a steelsleeve was used. The latter was heated in a bomb furnace with mechanicalshaking. The following examples will serve to illustrate the procedures.

EXAMPLE 4 Homopoly(Trimethyl late) A mixture of trimethyll-butene-2,3,4-tricarboxylate (4.6 g) and acetyl peroxide (1 ml of a 25percent solution in dimethyl phthalate) was placed in a 50 ml roundbottomed flask fitted with a rubber septum, degassed as described underExample 1. The flask was heated at 50 until a highly viscous materialwas obtained (24 hr.). The rubber septum was replaced by an adaptedl-Butene-2,3 ,4-Tricarboxytube and the latter connected through adry-ice trap to a vacuum pump. The flask was then heated to 180 withstirring and the low boiling fractions removed under a pressure of 0.1mm. At room temperature residual mass was a tough plastic glass; Yield 3g.

EXAMPLE tions removed at 180/0.1 mm. The yield was quantitative.

HYDROLYSIS The esters of the polymeric alkenepolycarboxylic acids werehydrolyzed by boiling their solutions in a minimum quantity ofacetone-water-concentrated hydrochloric acid=l2: l :1 mixture underreflux for 2-6 hr. The solvents were then removed under reducedpressure, the residue dissolved in water, the solution filtered toremove any insoluble material and evaporated to dryness in vacuo. Theresidue was washed with acetone and dried at 65/0.l mm. The following isa typical example.

EXAMPLE 6 EXAMPLE 7 l-Butene-2,3,4-tricarb0xylic Acid and Itaconic Acid1:1 Copolymer Trimethyl 1-butene-2 ,3 ,4-tricarboxylate wascopolymerized with itaconic anhydride as described in Example 3. Asuspension of l g of this polymer in 100 ml of 5 percent aqueoushydrochloric acid was stirred at until a clear solution resulted (12hr.). The solution was evaporated to dryness under reduced pressure andthe residual white solid washed with acetone and dried at 65/0.l mm.Yield: 0.7 g of the title compound.

EXAMPLE 8 l-Butene-2,3,4-tricarboxylic Acid-Itaconic Acid (1:1)Copolymer A solution of l-butene-2,3,4-tricarboxylic acid (9.4 g),itaconic acid (6.5 g), in freshly distilled water (50 ml), was placedtogether with a solution of potassium persulfate (0.16 g) in water (8ml) in a ml polymerization bottle fitted with a rubber septum. Theaqueous mixture was degassed by repeated freezing and evacuation, and asolution of sodium metabisulfite (0.08 g) in water (8 ml) introducedthrough a hypodermic syringe. The bottle was warmed to room temperature,filled with nitrogen and the contents stirred until a clear solutionresulted (seven days). The

solution was concentrated to half its original volume in vacuo and thepolymer precipitated by pouring the solution into acetone (1 liter). Thewhite precipitate was filtered and washed several times with acetone andthen dried at 65/0.1 mm for 3 hr. Yield: 11 g.

EXAMPLE 9 Preparation of Sodium Salts of Polymeric AlkenepolycarboxylicAcids The sodium salts for builder evaluation of the polymericalkenepolycarboxylic acids were prepared by neutralizing a saturatedaqueous solution of the poly-acid with 30 percent aqueous sodiumhydroxide until a pH of 9.5 was reached. The solution was thenconcentrated to half the original volume and poured into a largequantity of acetone to precipitate the sodium salt. The salt wasfiltered and dried at 65/0. 1 mm.

EXAMPLE DETERGENT FORMULATION This example illustrates typical detergentformulations of this invention as well as the excellent launderingproperties exhibited by these products.

The general detergent formulation which was utilized in this example isas follows:

Sodium linear alkylarenesulfonate Parts 20.0 Builder 50.0 (or 25) Sodiummetasilicate S-hydrate 12.0 Sodium carboxymethylcellulose 0.5

Sodium sulfate 17.5 (or 42.5)

In each instance the formulation was prepared by merely blending thevarious ingredients.

A variety of the novel builders were respectively substituted into thedetergent formulation. In order to determine the performancecharacteristics of the resulting detergent formulations, they weresubjected to the following test procedures.

Reflectance readings on the washed swatches were then taken from aHunter Reflectometer, Model Dl0. The results were expressed in terms ofpercent reflectance with the arbitrary standard of 100 percentreflectance being established for the reflectance value obtained on acotton swatch which had been washed with the standard detergentformulation containing 50 percent sodium tripolyphosphate builder inwater of 150 ppm hardness.

REDEfOSlTlON TEST The basic functions of a detergent solution may beconveniently divided into two distinct operations. First, removal ofsoil from the substrate and suspension thereof in the detergentsolution, and second, prevention of redeposition of the suspended soil.Redeposited soil is more tenaciously held on the fabric surface and isdifficult to remove by subsequent washings. As a result a builtdetergent formulation which causes considerable redeposition may stillwash fabrics brighter in the first few washings but gradually impart apermanent yellow or grey cast on the fabric. The redeposition test isintended to show the ability of the detergent formula tion to preventredeposition of soil during the wash as well as the rinse cycle. Theredeposition data are decreases in reflectance (AR) of unsoiled swatcheswhen washed with standard soiled swatches. In the test procedure, oneunsoiled swatch and three soiled swatches of each fabric type are washedthree times in a Terg-O-Tometer using freshly soiled swatches eachcycle. Conditions are otherwise the same as those used in the DetergencyTest. The detergency test results are summarized in Table 1 below.

TABLE I lgertignt Detergeney-percent 01 standard Redep0sitionAreflectance units 1.11 er in for- Water Cotton- Cotton- Cotton-Cottonmulated hardness B dacron daeron dacron dacron Builder; examplesdetergent (in p.p.m.) Cotton 50:50 :65 Nylon Cotton :50 35:65 Nylon (11)Sodium salt of 121:1 copoly BTCA AA-IA 50 300 101 93 98 104 1. l 4. 3 6.3 6.1 (12) Sodium salt of homopoly BTGA 50 300 79 80 78 0. 7 4. 6 6. 011. 6 (13) Sodium salt of 5:2 copoly BTCA- MVE b 50 300 78 77 80 70 1. 84. 4 5. 0 11. 2 (14) Sodium salt of 2:1 copoly BTCA- MAA 50 300 82 '8486 75 1.2 2.3 1.1 3.3 (15) Sodium salt of 1:1 copoly BTCA- MAA 50 300 8284 84 74 1.1 2.1 2. 4 11. 6 (16) Sodium salt of 1:111 eopoly BTCA- MA-AA50 300 7 85 87 84 0. 9 .2. 2 1. 7 2. 9 (17) Sodium Salt of2:1 copolyBTCA-AA. 25 150 98 82 86 92 1. 5 10. 0 9.0 7. 8 (18) Sodium salt of 1:1copoly BTCA-IA. 50 300 97 93 95 97 0.8 3. 1 6.3 3. 3 (19) Sodium Salt of1:1 copoly BTCA-IA. 25 150 103 74 77 91 1.1 16. 7 18.9 8. 3 Comparisondata Hardness of washing water. Not corrected for water (10? w./w.)present in builder. 0 Not corrected for water (17 w./w.) present inbuilder.

DETERGENCY TEST I 1.5; detergent formulation concentration of 0.15percent; temperature of F.; and a pH level of 9.5; washing time 10minutes; rinsing time 2 minutes.

B'ICA=1-butene-2,3A-trlcnrboxylle acid; AA=acry1ic acid; IA=lta conicacid; MAA=mcthacry1ic acid; MVE=mcthyl vinyl ether; SIP P= sodiumtripolyphosphatc.

The results presented in Table 1 clearly indicate the effectivelaundering characteristics exhibited by detergent formulationscontaining our novel builders.

It should be noted that comparable performance results may be obtainedby replacing the sodium linear alkylarenesulfonate in the abovedetergent formulation with any of the other surface active agentspreviously listed.

SEQUESTERING CAPACITY Since the ability to sequester calcium ions is acritical feature of an effective detergent builder, the various newbuilders were subjected to the following test procedures in order todetermine their sequestering capacity. Thus, an aqueous solution of thesample was 13 14 titrated potentiometrically with a standard calciumWhat is claimed is: nitrate solution at a pH of 10.0 and a temperatureof 17 A aliphatic polycarboxylic acid polymer exhibiting 25C. using adivalent cation activity electrode (Orion detergent builder propertiesselected from the class Research, Inc.) as the indicator electrode.consisting of: l-butene-2,3,4-tricarboxylic acid- The sequesteringcapacity was expressed as itaconic acid-acrylic acid (1:1:1) copolymer;copoly( 1- Ca g/ 100 g= (4.008 M V)/ W butene-2,3,4-tricarboxylic aciditaconic acid) (1:1) or where (2:1) or (1:2);copoly(1-butene-2,3,4-tricarboxylic M molarity of the calcium nitratesolution acid-maleic acid) (1:1); copoly( l-butene-2,3,4-tricar- Vvolume of the above solution required to reach boxylic acid-maleic acidacrylic acid) (1:1:1) and the inflexion point, andcopoly(l-butene-2,3,4-tricarboxylic acid-itaconic acid W= weight of thesample maleic acid) (1:1:1). Each of the builders tested was preparedaccording 2. An aliphatic polycarboxylic acid according to to theprocedures set forth in Examples 1 to 9, herein claim 1 having the name,l-butene-2,3,4-tricarboxylic above. The preparative procedures andsequestering acid-itaconic acid-acrylic acid (l:1:1)copolymer. capacityof some of these builders are presented in the 3. An aliphaticpolycarboxylic acid according to following table: claim 1 having thename, copoly(1-butene-2,3,4-tricar- Homoand copolymers of 1-butene2,3,4-tricarboxylie acid and their calcium sequestering capacitiesSequestoring capacity Prepared from Co, Example Name (mononn-rs)lropnrntivn procedure (solvent, catalyst, temperature and time) gJlOU g.loly BTCA 'IMBTC llnlk Wilyllltlllltllllill A0202, 50. 24 hr.) and l1ylrolysis i5 Copoly BTCA lA (1:1) BTCA and IA Solution polymerization(wilt-or, KQS '()5N11ZS2()5I 26, 7 days).. 2 Copoly BTCA-[A (1:1) TMBTCand lAn Sol1nton1 pplymorization (benzene, 157.201, reflux, 4 111'.) and18. 0 y r0 ys s. Copoly BTCA-AA (2:1) BICA and AA... Solutionpolymerization (water, KzSzOg, 26, 7 days) 22. 2 Copoly BTCA-AA (211)..BTCA and AA. Solution polymerization (xylene, B2202, reflux, 5 hr.) 11.7 Copoly BTCA-AA (1:1).. BICA and AA Solution polymerization (water,X18208, 26, 18.4 Copoly BTCA-AA (121).. B'ICA and AA Solutionpolymerization (water, Kzs-gos, 70, 12. 6 Copoly BTCA-MAA (1:1) BTCA andMAA.. Solution polymerization (water, Kgszos, 26, 1'10. 0 CopolyBICA-MAA (2:1) B'ICA and MAA.. Solution polymerization (water, X25203,26, 13. 5 Copoly BTCA-MA (1:1) BTCA and MAn solllutionI polymerization(xylene, BZZOQ, reflux, 3 hr.) and 8.8 ydro ysis. Copoly BICA-MVE (5:2)TMBIO and MVE Bulk polymerization B2102, 100, 24 hr.) and hydrolysis...8.0 Copoly B'ICA-VA... 'IMBTC and VAe. Bulk polymerization B2203, 60; 16hr.) and hydrolysis 7.0 Copoly BTCA-AA-IA BTCA AA and IA.. Solutionpolymerization (water, KESQOG, 26, 5 days). 1-23 33 Copoly BTCA-AA-MA (1'IMBTC AA and MA Solution pclymerization (benzene, B2102, reflux, 12hr.) 13

TDetennined on sodium salt. conic anhydride; MA=rnaleic acid;MAA=methaerylie acid; MAn= BZ202=BOI1ZOYI peroxide; Aczoz=acetylperoxide; AA=acrylic acid; maleic anhydride; MVE=methyl vinyl ether;TMBTC=trirnethyl 1- BTCA=1-buter1e-2,3,-triearboxylie acid; IA=itaconieacid; IAn=itabutene-2,3,4-tricarboxylatc; VAc=viny1acotate; VAl=vinylalcohol.

These results clearly indicate the ability of the builboxylic aciditaconic acid) 1:1) or (2:1 or 1:2).

ders of the invention to effectively sequester calcium 4. An aliphaticpolycarboxylic acid according to ions. The results are especiallynoteworthy when comclaim 1 having the name, copoly(l-butene-2,3,4-tricarpared with the 10.90 g. Ca/ 100 g. sequesteringvalue 40 boxylic acid-maleic acid) (1:1).

for the sodium tripolyphosphate, the standard in the S. An aliphaticpolycarboxylic acid according to builder field. claim 1 having the name,copoly( l-butene-2,3,4-tricar- Summarizing, it is seen that thisinvention provides boxylic acid-maleic acid acrylic acid)(l:l:l).

effective detergent formulations utilizing the novel 6. An aliphaticpolycarboxylic acid according to builders therein. claim 1 having thename, copoly( l-butene-2,3,4-tricar- Variations may be made inproportions, procedures boxylic acid-itaconic acid maleic acid) (1:1:1).and materials without departing from the scope of the invention asdefined by the following claims.

Patent No. 3,717,616 D ted February 20, 1973 Inventor) Paritosh M.Chakrabarti et a l It is certified that error ap pears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

The title "POLYMERS OF lBUTENE-2,3, I-TRICARBOXYLIC ACID" should read--POLYMERS OF l-BUTENE-Z, 3, ITRICARBOXYLIC ACID AND THEIR USE ASDETERGENT BUILDERS.

Column 7, line 2 "sodiumi 3" should read --'-sodium 3.

Column 7, line 13 "-l-hydroxy" should read 2hydroXy-.

Column 7, line 'i'line'fshould read "like- Column 8, line 6 "home"should read homo-.

Column 8, line 6 1 "(Trimethyl" second occurrence should be omitted.

Column 9, line 67 "=/2=1:1)" should read --=(2=1:1)--.

Signed and sealed this 3rd day of December 1974.

(SEAL) AtteSt:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Y Commissioner ofPatents F ORM PC1-1050 (10-69) USCOMM-DC 60376-565 U. S. GOVIIINIINTPRINTING OFFICE II! O-Qli-JSI

1. A aliphatic polycarboxylic acid polymer exhibiting detergent builderproperties selected from the class consisting of:1-butene-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid (1:1: 1)copolymer; copoly(1-butene-2,3,4-tricarboxylic acid - itaconic acid)(1:1) or (2:1) or (1:2); copoly(1-butene-2,3,4-tricarboxylic acid-maleicacid) (1:1); copoly(1-butene-2,3,4-tricarboxylic acid-maleic acid -acrylic acid) (1:1:1) and copoly(1-butene-2,3,4-tricarboxylicacid-itaconic acid - maleic acid) (1:1:1).
 2. An aliphaticpolycarboxylic acid according to claim 1 having the name,1-butene-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid (1:1:1)copolymer.
 3. An aliphatic polycarboxylic acid according to claim 1having the name, copoly(1-butene-2,3,4-tricarboxylic acid - itaconicacid) (1:1) or (2:1) or (1:2).
 4. An aliphatic polycarboxylic acidaccording to claim 1 having the name,copoly(1-butene-2,3,4-tricarboxylic acid-maleic acid) (1:1).
 5. Analiphatic polycarboxylic acid according to claim 1 having the name,copoly(1-butene-2,3,4-tricarboxylic acid-maleic acid -acrylicacid)(1:1:1).